Titanium or titanium alloy-and-resin composite and method for making the same

ABSTRACT

A method for making a titanium-and-resin composite or titanium alloy-and-resin composite includes: providing a titanium or titanium alloy substrate; electrochemically treating the substrate to form a titanium hydride layer; anodizing the substrate having the titanium hydride layer to form an nano-porous oxide film on the surface of the substrate, the nano-porous oxide film having nano pores and comprising at least two layers of different porosity or pore diameters; and inserting the substrate in a mold and melting resin on the surface of the nano-porous oxide film to form the composite.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No. 13/293507, filed Nov. 10, 2011, the contents of which are hereby incorporated by reference. The patent application Ser. No. 13/293507 in turn claims the benefit of priority under 35 USC 119 from Chinese Patent Application 201110135328.0, filed on May 24, 2011.

This application is one of the two related co-pending U.S. patent applications listed below. All listed applications have the same assignee. The disclosure of each of the listed applications is incorporated by reference into another listed application.

Attorney Docket No. Title Inventors US 39535 TITANIUM OR TITANIUM ALLOY- HUANN-WU AND-RESIN COMPOSITE AND CHIANG et al. METHOD FOR MAKING THE SAME US 39536 TITANIUM OR TITANIUM ALLOY- CHENG-SHI AND-RESIN COMPOSITE AND CHENN et al. METHOD FOR MAKING THE SAME

BACKGROUND

1. Technical Field

The present disclosure relates to titanium or titanium alloy-and-resin composites, particularly to a titanium or titanium alloy-and-resin composite having high bonding strength between titanium or titanium alloy and resin, and a method for making the composite.

2. Description of Related Art

Adhesives, for combining heterogeneous materials in the form of a metal and a synthetic resin are in demand in a wide variety of technical fields and industries, such as the automotive and household appliance fields. However, the bonding strength of metal and resin is weak. Furthermore, adhesives are generally only effective in a narrow temperature range of about −50° C. to about 100° C., which means they are not suitable in applications where operating or environmental temperatures may fall outside the range. Due to the above, other bonding methods have been applied that do not involve the use of an adhesive. One example of such methods is by forming bonds through injection molding or other similar process. However, the bonding strength of the metal and resin can be further improved.

Therefore, there is room for improvement within the art.

BRIEF DESCRIPTION OF THE FIGURES

Many aspects of the disclosure can be better understood with reference to the following figures. The components in the figures are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of the disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.

FIG. 1 is a cross-sectional view of an exemplary embodiment of a titanium or titanium alloy-and-resin composite.

FIG. 2 is a scanning electron microscope view of an exemplary embodiment of a titanium or titanium alloy substrate being anodized.

FIG. 3 is a cross-sectional view of an exemplary embodiment of a titanium or titanium alloy substrate being electrochemically treated.

FIG. 4 is a cross-sectional view of a mold of the composite shown in FIG. 1.

DETAILED DESCRIPTION

FIG. 1 shows a titanium-and-resin composite or titanium alloy-and-resin composite (composite 100) according to an exemplary embodiment. The composite 100 includes a titanium or titanium alloy substrate 11, a nano-porous oxide film 12 formed on the substrate 11, and resin compositions 13 formed on the nano-porous oxide film 12.

The nano-porous oxide film 12 is titanium dioxide film. In this embodiment, the nano-porous oxide film 12 is formed by electrochemically treating the substrate 11 first, and then anodizing the substrate 11.

Referring to FIG. 2, the nano-porous oxide film 12 defines nano-pores 125. Referring also to FIG. 1, the nano-porous oxide film 12 includes at least two layers of different three-dimensional meshed structures. The two layers are an inner layer 121 near to the substrate 11 and a surface layer 123 far from the substrate 11. The nano-porous oxide film 12 has a total thickness of about 300 nm-500 nm, and the surface layer 123 has a thickness of about 80 nm-120 nm. The nano-pores of the inner layer 121 and the nano-pores of the surface layer 123 have different pore diameters. The pore diameter of the nano-pores of the inner layer 121 may be in a range of about 20 nm-50 nm. The pore diameter of the nano-pores of the surface layer 123 may be in a range of about 100 nm-150 nm.

The resin compositions 13 may be coupled to the surface of the nano-porous oxide film 12 by molding. During the molding process, molten resin coats the surface of the nano-porous oxide film 12 and fills the nano-pores 125, thus strongly bonding the resin compositions 13 to the nano-porous oxide film 12 and the substrate 11. Compared to the conventional injection molding process in which the titanium or titanium alloy substrate is not electrochemically treated and anodized, the composite 100 in this exemplary embodiment has a much stronger bond between the resin compositions 13 and the substrate 11 (about five times the bonding force). The resin compositions 13 may be made up of crystalline thermoplastic synthetic resins having high fluidity. In this exemplary embodiment, polyphenylene sulfide (PPS) and polyamide (PA) can be selected as the molding materials for the resin compositions 13. These resin compositions 13 can bond firmly with the nano-porous oxide film 12 and the substrate 11.

Auxiliary components may be added to the resins to modify properties of the resin compositions 13, for example, fiberglass may be added to the PPS. The fiberglass may have a mass percentage of about 30% with regard to the PPS and the fiberglass.

A method for making the composite 100 may include the following steps:

The titanium or titanium alloy substrate 11 is provided.

The substrate 11 is ultrasonically cleaned using anhydrous ethanol and acetone in that order, and then rinsed.

The substrate 11 is electrochemically treated. The electrochemical treating process may be carried out in an acid water solution containing sulfuric acid, or an acid water solution of sulfuric acid, with the substrate 11 being a cathode, and a stainless steel board being an anode. The sulfuric acid may have a molar concentration of about 0.5 mol/L-2 mol/L. The electric current density through the acid water solution is about 0.1 ampere per square decimeter (A/dm²)-5 A/dm². Electrochemically treating the substrate 11 may last for about 1 minute-10 minutes. Once electrochemically treated, a titanium hydride (TiH₂) layer 14 is formed on the substrate 11 (referring to FIG. 3). The titanium hydride layer 14 has a thickness of about 80 nm-120 nm, and a surface roughness (Ra) of about 0.3 μm-0.5 μm. Next, the substrate 11 having the titanium hydride layer 14 is rinsed in water and dried.

The substrate 11 having the titanium hydride layer 14 is anodized to form the nano-porous oxide film 12. The anodizing process may be carried out in an alkaline water solution containing sodium hydroxide (NaOH), or an alkaline water solution of sodium hydroxide, with the substrate 11 being an anode, and a stainless steel board being a cathode. The sodium hydroxide may have a molar concentration of about 4.5 mol/L-5.5 mol/L. The electric current density through the alkaline water solution is about 1-30 A/dm². Anodizing the substrate 11 may last for about 1 minute-10 minutes. Once anodized, the nano-porous oxide film 12 is formed on the substrate 11. Next, the substrate 11 having the nano-porous oxide film 12 is rinsed in water and dried.

During the anodizing process, the titanium hydride layer 14 is first converted to titanium dioxide and forms the surface layer 123 of the nano-porous oxide film 12. When the titanium hydride layer 14 is completely converted to titanium dioxide, the anodizing process is continued on the substrate 11 and forms the inner layer 121 of the nano-porous oxide film 12.

In the exemplary embodiment, the electrochemical treating process and the anodizing process are all carried out at a room temperature, that is, the acid and the alkaline water solutions are not heated.

The thickness of the titanium hydride layer 14 in this embodiment is only an example. The thickness of the titanium hydride layer 14 can be changed by adjusting the concentration of the acid water solution, the electric current density, and the duration time of the electrochemical treating process.

The structure and relative characters of the nano-porous oxide film 12 in this embodiment is only an example. The structure and the characters of the nano-porous oxide film 12 can be changed by adjusting the concentration of the alkaline water solution, the electric current density, and the duration time of the anodizing process.

The thicknesses of the inner layer 121 and the surface layer 123 of the nano-porous oxide film 12, and the pore diameter of the nano pores 125 can be changed by adjusting the parameters of the electrochemical treating process and the anodizing process. Furthermore, by adjusting the treatment parameters, a nano-porous oxide film having more than two layers of different three dimensional meshed structures can also be obtained.

Referring to FIG. 4, an injection mold 20 is provided. The injection mold 20 includes a core insert 23 and a cavity insert 21. The core insert 23 defines several gates 231, and several first cavities 233. The cavity insert 21 defines a second cavity 211 for receiving the substrate 11. The substrate 11 having the nano-porous oxide film 12 is located in the second cavity 211, and molten/melted resin is injected through the gates 231 to coat the surface of the nano-porous oxide film 12 and fill the nano-pores 125, and finally to fill the first cavities 233 to form the resin compositions 13, as such, the composite 100 is formed. The molten resin may be crystalline thermoplastic synthetic resins having high fluidity, such as PPS, or PA.

The shear strength of the composite 100 has been tested. The tests indicated that the shear strength of the composite 100 was 19 MPa-27 MPa. Furthermore, the composite 100 was subjected to a temperature humidity bias test (72 hours, 85° C., relative humidity: 85%) and a thermal shock test (48 hours, −40° C.-85° C., 4 hours/cycle, 12 cycles total), such testing did not result in decreased shear strength of the composite 100.

It is believed that the exemplary embodiment and its advantages will be understood from the foregoing description, and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the disclosure or sacrificing all of its advantages, the examples hereinbefore described merely being preferred or exemplary embodiment of the disclosure. 

What is claimed is:
 1. A method for making a titanium or titanium alloy-and-resin composite, comprising: providing a titanium or titanium alloy substrate; electrochemically treating the substrate to form a titanium hydride layer on a surface thereof; anodizing the substrate having the titanium hydride layer to form an nano-porous oxide film on the surface of the substrate, the nano-porous oxide film having nano pores and comprising at least two layers of different porosity or pore diameters; and inserting the substrate in a mold and melting resin on the surface of the nano-porous oxide film to form the composite.
 2. The method as claimed in claim 1, wherein electrochemically treating the substrate is carried out in an acid water solution containing sulfuric acid for about 1-10 minutes with the substrate being a cathode, the molar concentration of the sulfuric acid is about 0.5 mol/L-2 mol/L, the electric current density through the acid water solution is about 0.1 A/dm²-5 A/dm².
 3. The method as claimed in claim 2, wherein the titanium hydride layer has a thickness of about 80 nm-120 nm and a surface roughness of about 0.3 μm-0.5 μm.
 4. The method as claimed in claim 1, wherein anodizing the substrate is carried out in an alkaline water solution containing sodium hydroxide for about 1 minute-10 minutes with the substrate being an anode, the mol concentration of the sodium hydroxide is about 4.5 mol/L-5.5 mol/L, the electric current density through the alkaline water solution is about 1 A/dm²-30 A/dm².
 5. The method as claimed in claim 1, wherein the resin is crystalline thermoplastic synthetic resin.
 6. The method as claimed in claim 5, wherein the crystalline thermoplastic synthetic resin is polyphenylene sulfide or polyamide.
 7. The method as claimed in claim 5, wherein the crystalline thermoplastic synthetic resin is polyphenylene sulfide added with fiberglass, the fiberglass has a mass percentage of about 30% with regard to the polyphenylene sulfide and the fiberglass.
 8. The method as claimed in claim 1, wherein the nano-porous oxide film is titanium dioxide film.
 9. The method as claimed in claim 1, wherein the at least two layers comprising an inner layer near the substrate and a surface layer away from the substrate, the inner layer comprising nano pores having a pore diameter at a range of about 20 nm-50 nm, the surface layer comprising nano pores having a pore diameter at a range of about 100 nm-150 nm.
 10. The method as claimed in claim 9, wherein the nano-porous oxide film has a total thickness of about 300 nm-500 nm, the surface layer has a thickness of about 80 nm-120 nm.
 11. The method as claimed in claim 9, wherein the resin composition fills the nano-pores of the inner layer and the surface layer. 